Metal-oxygen battery and components thereof

ABSTRACT

A metal-oxygen battery and components of a metal-oxygen battery can include sulfamide, sulfoxy, carbonyl, phosphoramide or heterocyclic groups.

CLAIM OF PRIORITY

This application claims priority to U.S. Provisional Application No.62/685,263, filed Jun. 14, 2018, which is incorporated by reference inits entirety.

TECHNICAL FIELD

The invention relates to a metal-oxygen battery and components of ametal-oxygen battery.

BACKGROUND

Lithium-oxygen (Li—O₂) batteries show great promises in energy storageand transportation applications.

SUMMARY

Aprotic lithium-oxygen (Li—O₂) battery show great promises in energystorage and transportation applications owing to their high gravimetricenergies that potentially represent a 3 to 5 times increase overlithium-ion batteries.

Solvents and polymers for a metal-oxygen battery can include an organicsulphur or nitrogen-containing component. The component can be aprotic.

In general, a composition can include a polyolefin including a pluralityof functional groups, the functional groups including an aprotic polargroup selected from the group consisting of sulfamide, sulfoxy,carbonyl, phosphoramide or heterocyclic groups.

In one aspect, a composition can include a polyolefin including aplurality of functional groups, the functional groups including anaprotic polar group selected from the group consisting of sulfamide,sulfoxy, carbonyl, phosphoramide or heterocyclic groups.

In certain circumstances, the polyolefin can include a polymer blockselected from the group consisting of:

In certain embodiments, n can be 1 to 100,000, less than 50,000, lessthan 25,000, less than 20,000, less than 10,000, or less than 1,000. Inother embodiments, n can be greater than 10, greater than 25, greaterthan 40, greater than 50, greater than 100, greater than 200, or greaterthan 250. In certain embodiments, X can be a functional group includingone or more sulfamide, sulfoxy, carbonyl, phosphoramide or heterocyclicgroups. In certain embodiments, Y can be a bond or a C1-C6 alkyl oralkenyl optionally interrupted by O, S or NR, where NR is N—C1-C6 alkyland including a moiety having one or more functional group includingsulfamide, sulfoxy, carbonyl, phosphoramide or heterocyclic groups.

In certain circumstances, X can be a monovalent or divalent moietyhaving a structure selected from the group consisting of

The monovalent moiety can be covalently bonded to the polymer at asingle connection point. The divalent moiety can be covalently bonded tothe polymer at two connection points, for example, in the polymer chainbackbone.

In certain circumstances, Y can be a bond, in which case a functionalgroup, for example, a polar aprotic group, is bonded directly to apolymer backbone.

In certain circumstances, Y can be a C1-C6 alkyl or alkenyl optionallyinterrupted by O, S or NR, where NR is N—C1-C6 alkyl, in which case afunctional group, for example, a polar aprotic group, is bonded directlyto an alkyl group pendant from polymer backbone

In certain circumstances, the polyolefin can include a polymer blockselected from the group consisting of:

In another aspect, a battery can include a composition as describedherein.

In another aspect, a battery can include a solvent including an aproticpolar group.

In certain circumstances, the aprotic polar group includes sulfamide,sulfoxy, carbonyl, phosphoramide or heterocyclic groups.

In certain circumstances, the solvent, or the aprotic polar group caninclude

In certain circumstances, the battery can include a lithium saltelectrolyte.

Other features, objects, and advantages will be apparent from thedescription, drawings, and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts synthesis of aprotic solvents, for example, sulfamide-and sulfonamide-based solvents, BTMSA, BMCF3 SA, and DMCF3 SA.

FIG. 2 depicts properties of aprotic solvents. Panel (a) shows themeasured chemical shifts of ²³Na NMR signal of 20 mM NaTFSI in BTMSA,DMCF₃SA, and BMCF₃SA compared to that of DMSO, DMF, DME, and PC. The²³Na signal from the internal standard, 0.5 M NaClO₄ in H₂O, is set to 0ppm. Panel (b) shows a linear trend line, indicated by the dashed line,correlating the DNs of DMSO (29.8), DMF (26.6), DME (20.2), and PC(15.1) and their measured relative ²³Na NMR shifts was used to estimatethe DNs of BTMSA, DMCF₃SA, and BMCF₃SA, which were determined to be16.9, 16.4, and 13.3, respectively. Panel (c) shows conductivity ofsolutions containing 0.1 M LiTFSI in BTMSA, DMCF₃SA, and BMCF₃SAcompared to that of tetraglyme (G4) as a commercial reference at varioustemperatures.

FIG. 3 depicts potentiostatic electrochemical stability tests ofelectrolytes containing 0.1 M LiTFSI in BTMSA, DMCF₃SA, and BMCF₃SAcompared to DMSO at potential ≤4.5 V_(Li). Panel (b) shows an enlargedview of a portion of panel (a). Panel (c) shows oxidative current atpotential ≥4.8 V_(Li).

FIG. 4 depicts galvanostatic discharge/charge (0.03 mA/cm₂) curves andgas evolution rates on charge of Li—O₂ cells containing 0.2 M LiTFSI inpanel (a) DMSO, panel (b) DMCF₃SA, and panel (c) BMCF₃SA.

FIG. 5 depicts discharge data. Panel (a) shows galvanostatic discharge(0.03 mA/cm²) and charge (0.02 mA/cm²) profiles of select cycles (1st,5th, 10th, 25th, 50th, and 80th cycles) of a Li—O₂ cell employing 0.2 MLiTFSI in DMCF₃SA as the electrolyte. (b) ¹H NMR analyses on DMCF₃SA-(denoted by “DM” for brevity), G4-, and DMSO-based electrolytescollected after select cycles (denoted by “_cycle#”).

FIG. 6 depicts properties of solvent. Panel (a) shows molecularstructures of compounds considered in the computational investigationwhere each inequivalent hydrogen is labeled. Panel (b) shows adiabatic−G_(ox) and V_(ox) of the compounds shown in panel (a) computed usingB3LYP/6-311++G(d,p) with geometries optimized at B3LYP/6-31G(d,p) inimplicit DMSO solvent. The experimentally measured scale versus Li/Li⁺,plotted on the right axis, was obtained from the oxidation energy in eVby the subtraction of 1.4 V. Panel (c) shows bond dissociation energiesand panel (d) shows deprotonation free energies of all inequivalent C—Hbonds shown in panel (a) computed at the B3LYP/6-31G(d,p) level oftheory in implicit DMSO solvent. Asterisk (*) indicates the estimatedelectronic deprotonation energies prior to elimination reaction (<10%bond elongation).

FIG. 7 depicts Raman spectra of pure BMCF₃SA and DMCF₃SA (denoted byBM-pure and DM-pure, respectively, for brevity) as well as 0.2 M LiTFSIin G4, BTMSA, DMCF₃SA, and BMCF₃SA (denoted by G4-LiTFSI, BTM-LiTFSI,DM-LiTFSI, and BM-LiTFSI, respectively) in the range of 700 to 780 cm¹measured at 25° C. The peak attributable to the S—N symmetric stretchingof TFSI anion, marked with vertical dashed lines, shifts to higher wavenumbers in BMCF₃SA and DMCF₃SA, indicating stronger ion association inthese two solvents.

FIG. 8 depicts ¹H NMR analyses of the chemical stability of: panel (a)BTMSA, panel (b) DMCF₃SA, panel (c) BMCF₃SA, and panel (d) DMSO. Tealand red spectra were obtained before and after the chemical stabilitytest, in which the samples were mixed with 0.5 equiv. commercial Li₂O₂and KO₂ powders. The mixtures were stirred and maintained at 80° C. forthree days.

FIG. 9 depicts characteristics of discharge electrodes. Panel (a) showsXRD characterization of the full discharge electrodes in electrolytescontaining 0.2 M LiTFSI in BTMSA, DMCF₃SA, and BMCF₃SA. The presence ofLi₂O₂, albeit of relatively low intensity, was detected for all threedischarged electrodes. Panel (b) shows FTIR spectra of electrolytescollected after full discharge (denoted by D followed by the solvent,BTM=BTMSA, DM=DMCF₃SA, and BM=BMCF₃SA) compared to the pristineelectrolytes (denoted by P). No noticeable change was observed for allthree electrolyte solvents. Panel (c) shows ¹H NMR and panel (d) shows¹⁹F NMR analyses on electrolytes collected after full discharge (red)compared to the pristine electrolyte solvents (teal). No noticeablechange was observed for all three electrolytes.

FIG. 10 depicts electrochemical stability of electrolytes containing 0.1M LiTFSI in G4 and BMCF₃SA. Panel (a) shows potentiostatic testsperformed in O₂. Inset: oxidative current recorded at potential ≥4.8V_(Li). Panel (b) shows a cyclic voltammogram (CV, 1 mV/s) between 2.0and 5.0 V_(Li) was performed in Ar. Inset: linear sweep voltammogram(LSV, 0.1 mV/s) from open circuit voltage to 5.0 V_(Li) in O₂. Panel (c)shows galvanostatic discharge and charge (0.03 mA/cm²) curves and panel(d) shows O₂ evolution rate on charge of Li—O₂ cell containing 0.2 MLiTFSI in G4.

FIG. 11 depicts electrochemical stability of electrolytes containingElectrochemical stability of electrolytes containing 0.1 M LiTFSI inBTMSA, DMCF₃SA, and BMCF₃SA compared to DMSO as a commercial reference.Cyclic voltammogram (CV, 1 mV/s) between 2.0 and 5.0 V_(Li) in Ar.Inset: linear sweep voltammogram (LSV, 0.1 mV/s) from open circuitvoltage to 5.0 V_(Li) in O₂.

FIG. 12 depicts galvanostatic discharge/charge (0.03 mA/cm²) curves andgas evolution rates on charge of a Li—O₂ cell containing 0.2 M LiTFSI inG4.

FIG. 13 depicts properties of DMCF₃SA. Panel (a) shows ¹H NMR, panel (b)shows ¹⁹F NMR and panel (c) shows FTIR analyses on electrolytes (0.2 MLiTFSI in DMCF₃SA, denoted by DM for brevity, G4 and DMSO) collectedafter select galvanostatic cycles (denoted by “_cycle#”).

FIG. 14 depicts properties of DMCF₃SA. Panel (a) shows ¹H NMR and panel(b) shows ¹⁹F NMR analyses on extracted positive electrodes of cellscontaining 0.2 M LiTFSI in DMCF₃SA, denoted by DM for brevity, G4 andDMSO after select galvanostatic cycles (denoted by “_cycle#”).

FIG. 15 depicts a battery.

FIG. 16 depicts synthetic schemes to compounds described herein.

FIGS. 17-19 depict properties of compounds described herein.

FIGS. 20-21 depict polymers described herein.

FIGS. 22-23 depict synthetic schemes to compounds and polymers describedherein.

FIG. 24 depicts properties of polymers described herein.

FIG. 25 depicts synthetic schemes to compounds and polymers describedherein.

FIGS. 26-27 depict properties of polymers described herein.

FIGS. 28-29 depict properties of batteries with polymers describedherein, with different ratios of electrolyte to monomer groups.

FIG. 30 depicts synthetic schemes to compounds described herein.

FIG. 31 depicts properties of compounds described herein.

FIG. 32 depicts synthetic schemes to polymers described herein.

FIGS. 33-34 depict properties of polymers described herein.

FIG. 35 depicts synthetic schemes to polymers described herein.

FIGS. 36-38 depict properties of polymers described herein.

FIG. 39 depicts synthetic schemes to polymers described herein.

FIGS. 40-47 depict properties of polymers and batteries including thepolymers described herein.

FIG. 48 depicts a synthetic scheme and properties of polymers describedherein.

FIGS. 49-50 depict properties of polymers and batteries including thepolymers described herein.

FIG. 51 depicts properties of solvents described herein.

DETAILED DESCRIPTION

Electrolyte instability is one of the most challenging impediments topractical Lithium-Oxygen (Li—O₂) battery operations. Sulfamide- andsulfonamide-based solvents can be designed for chemical andelectrochemical oxidative stability in aprotic Li—O₂ batteries. Allthree solvents were found to be stable against lithium peroxide andpotassium superoxide powders at 80° C. and under full dischargeconditions. Sulfonamide-based solvents with electron-withdrawingtrifluoromethyl functional group were found to be considerably stableagainst oxidation (V_(ox)>4.5 V_(Li)). Differential electrochemical massspectrometry measurements showed oxygen as the vastly predominant gasevolved on charge. Results presented in this study demonstrate thatsulfonamide-based solvents with thoughtfully designed molecularstructures are promising candidates for aprotic Li—O₂ batteryelectrolytes.

Aprotic lithium-oxygen (Li—O₂) battery show great promises in energystorage and transportation applications owing to their high gravimetricenergies that potentially represent a 3 to 5 times increase overlithium-ion batteries. See, for example, Lu, J.; Li, L.; Park, J.-B.;Sun, Y.-K.; Wu, F.; Amine, K. Aprotic and Aqueous Li—O 2 Batteries.Chem. Rev. 2014, 114 (11), 5611-5640; Lu, Y.-C.; Gallant, B. M.; Kwabi,D. G.; Harding, J. R.; Mitchell, R. R.; Whittingham, M. S.; Shao-Horn,Y. Lithium-Oxygen Batteries: Bridging Mechanistic Understanding andBattery Performance. Energy Environ. Sci. 2013, 6 (3), 750-768;Christensen, J.; Albertus, P.; Sanchez-Carrera, R. S.; Lohmann, T.;Kozinsky, B.; Liedtke, R.; Ahmed, J.; Kojic, A. A Critical Review ofLi/Air Batteries. J. Electrochem. Soc. 2012, 159 (2), R1; and Abraham,K. M.; Jiang, Z. A Polymer Electrolyte—Based Rechargeable Lithium/OxygenBattery TECHNICAL PAPERS ELECTROCHEMICAL SCIENCE AND TECHNOLOGY APolymer Electrolyte-Based Rechargeable Lithium/Oxygen Battery. J.Electrochem. Soc. 1996, 143 (1), 1-5, each of which is incorporated byreference in its entirety. The stable and reversible operation oflithium-oxygen (Li—O₂) batteries is currently hindered by severeelectrolyte degradation. Common non-aqueous solvents, includingcarbonates, glymes, dimethyl sulfoxide (DMSO), and dimethylformamide(DMF), have been shown to decompose in the presence of reactive oxygenreduction products. See, for example, Freunberger, S. A.; Chen, Y.;Peng, Z.; Griffin, J. M.; Hardwick, L. J.; Bardé, F.; Novák, P.; Bruce,P. G. Reactions in the Rechargeable Lithium-O2 Battery with AlkylCarbonate Electrolytes. J. Am. Chem. Soc. 2011, 133 (20), 8040-8047;MIZUNO, F.; NAKANISHI, S.; KOTANI, Y.; YOKOISHI, S.; IBA, H.Rechargeable Li-Air Batteries with Carbonate-Based Liquid Electrolytes.Electrochemistry 2010, 78 (5), 403-405; Xu, W.; Xu, K.; Viswanathan, V.V; Towne, S. A.; Hardy, J. S.; Xiao, J.; Nie, Z.; Hu, D.; Wang, D.;Zhang, J. Reaction Mechanisms for the Limited Reversibility of Li—O2Chemistry in Organic Carbonate Electrolytes. J. Power Sources 2011, 196(22), 9631-9639; Bryantsev, V. S.; Blanco, M. Decomposition of OrganicCarbonate-Based Electrolytes. J. Phys. Chem. Lett. 2011, 379-383;Freunberger, S. A.; Chen, Y.; Drewett, N. E.; Hardwick, L. J.; Bardé,F.; Bruce, P. G. The Lithium-Oxygen Battery with Ether-BasedElectrolytes. Angew. Chemie—Int. Ed. 2011, 50 (37), 8609-8613;McCloskey, B. D.; Bethune, D. S.; Shelby, R. M.; Mori, T.; Scheffler,R.; Speidel, A.; Sherwood, M.; Luntz, A. C. Limitations inRechargeability of Li—O 2 Batteries and Possible Origins. J. Phys. Chem.Lett. 2012, 3 (20), 3043-3047; Wang, H.; Xie, K. Investigation of OxygenReduction Chemistry in Ether and Carbonate Based Electrolytes for Li—O2Batteries. Electrochim. Acta 2012, 64, 29-34; Kwabi, D. G.; Batcho, T.P.; Amanchukwu, C. V.; Ortiz-Vitoriano, N.; Hammond, P.; Thompson, C.V.; Shao-Horn, Y. Chemical Instability ofDimethyl Sulfoxide inLithium-Air Batteries. J. Phys. Chem. Lett. 2014, 5 (16), 2850-2856;Mozhzhukhina, N.; Mendez De Leo, L. P.; Calvo, E. J. InfraredSpectroscopy Studies on Stability of Dimethyl Sulfoxide for Applicationin a Li-Air Battery. J. Phys. Chem. C 2013, 117 (36), 18375-18380,Gampp, H.; Lippard, S. J. Reinvestigation of 18-Crown-6 Ether/PotassiumSuperoxide Solutions in Me2SO. Inorg. Chem. 1983, 22 (2), 357-358; Chen,Y.; Freunberger, S. A.; Peng, Z.; Bardé, F.; Bruce, P. G. Li—O 2 Batterywith a Dimethylformamide Electrolyte. J. Am. Chem. Soc. 2012, 134 (18),7952-7957, each of which is incorporated by reference in its entirety.Given the radical-rich, basic, nucleophilic and oxidizing environment ofthe oxygen electrode, the design for stable electrolytes in aproticLi—O₂ batteries must eliminate or minimize chemical moieties prone tohydrogen abstraction, deprotonation, nucleophilic substitution as wellas electrochemical oxidation. See, for example, Feng, S.; Chen, M.;Giordano, L.; Huang, M.; Zhang, W.; Amanchukwu, C. V.; Anandakathir, R.;Shao-horn, Y.; Johnson, J. A. Mapping a Stable Solvent StructureLandscape for Aprotic Li-Air Battery Organic Electrolytes. J. Mater.Chem. A 2017, 5 (45), 23987-23998, which is incorporated by reference inits entirety. In an early attempt, by substituting the secondaryhydrogens of 1,2-dimethoxyethane (DME) with methyl groups (—CH₃) withthe aim of improving stability against hydrogen abstraction, Nazar etal. observed improved cycling stability of the substituted solvent overDME. See, for example, Adams, B. D.; Black, R.; Williams, Z.; Fernandes,R.; Cuisinier, M.; Berg, E. J.; Novak, P.; Murphy, G. K.; Nazar, L. F.Towards a Stable Organic Electrolyte for the Lithium Oxygen Battery.Adv. Energy Mater. 2015, 5 (1), which is incorporated by reference inits entirety. More recently, to improve stability against deprotonationand nucleophilic substitution, Aurbach and coworkers designed a newketone-based solvent, 2,4-dimethoxy-2,4-dimethylpentan-3-one (DMDMP),which lacks acidic α-proton or good leaving groups upon nucleophilicattack, and reported small amounts of decomposition products after 48cycles. See, for example, Sharon, D.; Sharon, P.; Hirshberg, D.; Salama,M.; Afri, M.; Shimon, L. J. W.; Kwak, W. J.; Sun, Y. K.; Frimer, A. A.;Aurbach, D. 2,4-Dimethoxy-2,4-Dimethylpentan-3-One: An Aprotic SolventDesigned for Stability in Li—O2Cells. J. Am. Chem. Soc. 2017, 139 (34),11690-11693, which is incorporated by reference in its entirety. Withsimilar design principles, a new pivalate-based solvent, free of acidicα-proton prone to deprotonation or vulnerable α-carbon againstnucleophilic substitution, was found to be stable in the presence ofpotassium superoxide (KO₂) for at least 120 hours and after 11 cycles.See, for example, Li, T.; Wang, Z.; Yuan, H.; Li, L.; Yang, J. A MethylPivalate Based Electrolyte for Non-Aqueous Lithium-oxygen Batteries.Chem. Commun. 2017, 53 (75), 10426-10428, which is incorporated byreference in its entirety.

In one aspect, a composition can include a polyolefin including aplurality of functional groups, the functional groups including anaprotic polar group selected from the group consisting of sulfamide,sulfoxy, carbonyl, phosphoramide or heterocyclic groups.

In certain circumstances, the polyolefin can include a polymer blockselected from the group consisting of:

In certain embodiments, n can be 1 to 100,000, less than 50,000, lessthan 25,000, less than 20,000, less than 10,000, or less than 1,000. Inother embodiments, n can be greater than 10, greater than 25, greaterthan 40, greater than 50, greater than 100, greater than 200, or greaterthan 250. In certain embodiments, X can be a functional group includingone or more sulfamide, sulfoxy, carbonyl, phosphoramide or heterocyclicgroups. In certain embodiments, Y can be a bond or a C1-C6 alkyl oralkenyl optionally interrupted by O, S or NR, where NR is N—C1-C6 alkyland including a moiety having one or more functional group includingsulfamide, sulfoxy, carbonyl, phosphoramide or heterocyclic groups.

In certain circumstances, X can be a monovalent or divalent moietyhaving a structure selected from the group consisting of

The monovalent moiety can be covalently bonded to the polymer at asingle connection point. The divalent moiety can be covalently bonded tothe polymer at two connection points, for example, in the polymer chainbackbone.

In certain circumstances, Y can be a bond, in which case a functionalgroup, for example, a polar aprotic group, is bonded directly to apolymer backbone.

In certain circumstances, Y can be a C1-C6 alkyl or alkenyl optionallyinterrupted by O, S or NR, where NR is N—C1-C6 alkyl, in which case afunctional group, for example, a polar aprotic group, is bonded directlyto an alkyl group pendant from polymer backbone

In certain circumstances, the polyolefin can include a polymer blockselected from the group consisting of:

In another aspect, a battery can include a composition as describedherein.

In another aspect, a battery can include a solvent including an aproticpolar group.

In certain circumstances, the aprotic polar group includes sulfamide,sulfoxy, carbonyl, phosphoramide or heterocyclic groups.

In certain circumstances, the solvent, or the aprotic polar group caninclude

In certain circumstances, the battery can include a lithium saltelectrolyte.

FIG. 15 schematically illustrates a metal-air battery 1, which includesanode 2, cathode 3, electrolyte 4, anode collector 5, and, optionally,cathode collector 6. The battery can include an electrolyte, forexample, a lithium salt.

Three solvents (see, FIG. 1), N,N-Dimethyl-N′-butyl-N′-methylsulfamide(BTMSA), N-butyl-N-methyl-trifluoromethanesulfonamide (BMCF₃SA), andN,N-dimethyl-trifluoromethanesulfonamide (DMCF₃SA), have been designedfor chemical and electrochemical stability in aprotic Li—O₂ batteries.Tetraalkylsulfamide solvents such as BTMSA are compatible with stronglybasic and nucleophilic reagents, which suggests they may exhibitpromising chemical stability in the oxygen electrode of typical aproticLi—O₂ battery. See, for example, Richey, H. G.; Farkas, J. Sulfamidesand Sulfonamides as Polar Aprotic Solvents. J. Org. Chem. 1987, 52 (4),479-483, which is incorporated by reference in its entirety. On theother hand, the electron-withdrawing trifluoromethyl (—CF₃) moiety wasintroduced in the sulfonamide-based solvents, BMCF₃SA and DMCF₃SA, toenhance their electrochemical oxidative stability. First, the stabilityof BTMSA and BMCF₃SA along with hexamethylphosphoramide (HMPA, acommercially available solvent whose stability in aprotic Li—O₂batteries was demonstrated recently) andN,N-dimethyl-t-butanesulfonamide (tBDMSA, replacing the —CF₃ in DMCF₃SAwith a t-butyl group) was assessed by a computational frameworkdeveloped to predict organic molecules' susceptibility toelectrochemical oxidation, hydrogen abstraction and deprotonation (FIG.6). See, for example, Zhou, B.; Guo, L.; Zhang, Y.; Wang, J.; Ma, L.;Zhang, W. H.; Fu, Z.; Peng, Z. A High-Performance Li—O2 Battery with aStrongly Solvating Hexamethylphosphoramide Electrolyte and aLiPON-Protected Lithium Anode. Adv. Mater. 2017, 29 (30), 2-7, which isincorporated by reference in its entirety. The electrochemical oxidationpotential calculations suggested that, as expected, the sulfonamide withelectron-withdrawing —CF₃ group, BMCF₃SA, is the most stable (i.e.,highest predicted oxidation potential), followed by the sulfonamide witht-butyl group, which in turn is more stable than tetraalkylsulfamideBTMSA, which bears strongly electron-donating moieties (FIG. 6, panelb). It is noted that the sulfamide (BTMSA) and sulfonamides (BMCF₃SA andtBDMSA) were predicted to have higher electrochemical oxidativestability than the commercial HMPA. Additionally, our computationalanalyses suggested that all four molecules considered are resistant tohydrogen and proton removal (FIG. 6, panels c-d). To experimentallyvalidate our predictions and further study the performance of thesesulfamide- and sulfonamide-based solvents, BTMSA was synthesized viacondensation of N,N-dimethylsulfonamoyl chloride and N-butylmethylaminein 90% yield, while BMCF₃SA and DMCF₃SA (a slight molecular variation ofBMCF₃SA by replacing the butyl group in BMCF₃SA with a methyl group)were prepared via condensation of trifluoromethanesulfonyl chloride andthe corresponding secondary amines in 80%-90% yields (FIG. 1). Thesethree solvents are clear, colorless liquids at room temperature; theirboiling temperature and viscosity are showed in Table 1.

TABLE 1 Estimated boiling points and viscosities of representativesolvents. Solvents BP (° C.) Viscosity (cP) BTMSA ≈220 3.56^(a) BMCF₃SA≈187 1.65^(b) DMCF₃SA ≈120 1.48^(b) ^(a)Estimated based on the similarchemical structure from Choquette, Y.; Brisard, G.; Parent, M.;Brouillette, D.; Perron, G.; Desnoyers, J. E.; Armand, M.; Gravel, D.;Slougui, N. Sulfamides and Glymes as Aprotic Solvents for LithiumBatteries. J. Electrochem. Soc. 1998, 145, 3500-3507, which isincorporated by reference in its entirety. ^(b)Values taken from Fu,S.-T.; Liao, S.-L.; Nie, J.; Zhou, Z.-B. N,N-dialkylperfluoroalkanesulfonamides: Synthesis, characterization and properties.J. Fluorine Chem. 2013, 147, 56-64, which is incorporated by referencein its entirety, or estimated based on similar chemical structure.tBDMSA and N-butyl-N-methyl-t-butanesulfonamide (tBBMSA, replacing oneof the methyl groups in tBDMSA with an N-butyl) were also synthesized.However, they are solid at room temperature (melting temperature >50°C.) and thus not suitable for room temperature Li—O₂ battery operation;tBDMSA and tBBMSA are excluded in further characterizations. In thiswork, to assess the suitability of BTMSA, DMCF₃SA, and BMCF₃SA aselectrolyte solvents in aprotic Li—O₂ batteries, we evaluated theirdonor numbers (DNs), conductivity, as well as chemical andelectrochemical stability. Furthermore, we studied the galvanostaticdischarge and charge behaviors, oxygen evolution profiles on charge, andcyclability of Li—O₂ cells containing sulfonamide-based electrolytes.Results presented in this study demonstrate that sulfonamide-basedsolvents with thoughtfully designed molecular structures are promisingcandidates for aprotic Li—O₂ battery electrolytes.

The DN of an electrolyte describes its ability to interact with Li⁺through donating electron density (i.e., Lewis basicity), which in turninfluences the solubility and life time of oxygen reduction reaction(ORR) intermediate, LiO₂, as well as the discharge product morphologyand capacity. See, for example, Gutmann, V. Solvent Effects on theReactivities of Organometallic Compounds. Coord. Chem. Rev. 1976, 18(2), 225-255, Younesi, R.; Veith, G. M.; Johansson, P.; Edström, K.;Vegge, T. Lithium Salts for Advanced Lithium Batteries: Li-metal, Li—O2, and Li—S. Energy Environ. Sci. 2015, 8 (7), 1905-1922; Abraham, K. M.Electrolyte-Directed Reactions of the Oxygen Electrode in Lithium-AirBatteries. J. Electrochem. Soc. 2014, 162 (2), A3021-A3031; Johnson, L.;Li, C.; Liu, Z.; Chen, Y.; Freunberger, S. A.; Ashok, P. C.; Praveen, B.B.; Dholakia, K.; Tarascon, J.-M.; Bruce, P. G. The Role of LiO2Solubility in O2 Reduction in Aprotic Solvents and Its Consequences forLi—O2 Batteries. Nat. Chem. 2014, 6 (12), 1091-1099, each of which isincorporated by reference in its entirety. The DNs of BTMSA, BMCF₃SA,and DMCF₃SA were estimated by ²³Na NMR. See, for example, Erlich, R. H.;Popov, A. I. Spectroscopic Studies of Ionic Solvation. X. Study of theSolvation of Sodium Ions in Nonaqueous Solvents by Sodium-23 NuclearMagnetic Resonance. J. Am. Chem. Soc. 1971, 93 (22), 5620-5623, which isincorporated by reference in its entirety. Solutions of 20 mM sodiumbis(trifluoromethanesulfonyl)imide (NaTFSI) were prepared in BTMSA,BMCF₃SA, DMCF₃SA as well as in DMSO, N-dimethylformamide (DMF), DME, andpropylene carbonate (PC) with 0.5 M sodium perchlorate (NaClO₄) indeionized water (H₂O) as the internal standard. The ²³Na NMR shifts ofNaTFSI in these seven solvents are shown in FIG. 2, panel a. Drawing alinear trend line correlating the reported DNs of DMSO (29.8), DMF(26.6), DME (20.2), and PC (15.1) and their ²³Na NMR shifts, the DNs ofBTMSA, DMCF₃SA, and BMCF₃SA were estimated to be 16.9, 16.4, and 13.3,respectively (shown in FIG. 2, panel b). See, for example, Erlich, R.H.; Popov, A. I. Spectroscopic Studies of Ionic Solvation. X. Study ofthe Solvation of Sodium Ions in Nonaqueous Solvents by Sodium-23 NuclearMagnetic Resonance. J. Am. Chem. Soc. 1971, 93 (22), 5620-5623; Linert,W.; Jameson, R. F.; Taha, A. Donor Numbers of Anions in Solution: TheUse of Solvatochromic Lewis Acid?Base Indicators. J. Chem. Soc. Dalt.Trans. 1993, No. 21, 3181; Burke, C. M.; Pande, V.; Khetan, A.;Viswanathan, V.; McCloskey, B. D. Enhancing Electrochemical IntermediateSolvation through Electrolyte Anion Selection to Increase NonaqueousLi—O 2 Battery Capacity. Proc. Natl. Acad. Sci. 2015, 112 (30),9293-9298; Cahen, Y. M.; Handy, P. R.; Roach, E. T.; Popov, A. I.Spectroscopic Studies of Ionic Solvation. XVI. Lithium-7 and Chlorine-35Nuclear Magnetic Resonance Studies in Various Solvents. J. Phys. Chem.1975, 79 (1), 80-85; Handy, P. R.; Popov, A. I. Spectroscopic Studies ofIonic Solvation-XII. Spectrochim. Acta Part A Mol. Spectrosc. 1972, 28(8), 1545-1553, each of which is incorporated by reference in itsentirety. As expected, solvents with electron-withdrawing —CF₃ grouphave lower donor abilities. The measured conductivities of solutionscontaining 0.1 M LiTFSI in BTMSA, BMCF₃SA, and DMCF₃SA at varioustemperatures are compared to that of tetraglyme (G4) as a commercialreference in FIG. 1, panel c. The solvent with the highest DN, BTMSA,exhibited conductivity approximately two times as high as G4, whereasDMCF₃SA, and BMCF₃SA showed lower conductivities, ˜2 and 5 times lowerthan that of BTMSA, respectively. We believe the lower conductivity ofDMCF₃SA, and BMCF₃SA can be attributed to weaker Li⁺ binding energies(ΔG_(binding)=G(Li⁺ . . . Solvent)−G(Li⁺)−G(Solvent), −5.6 and −5.1kJ/mol for DMCF₃SA, and BMCF₃SA, respectively, compared to −21.5 kJ/molin BTMSA). As expected, LiTFSI is less dissociative in BMCF₃SA, andDMCF₃SA, indicated by higher Raman shifts of the S—N symmetricstretching of TFSI anion (FIG. 7), leading to lower charge carrierconcentration and conductivity. See, for example, Tatara, R.; Kwabi, D.G.; Batcho, T. P.; Tulodziecki, M.; Watanabe, K.; Kwon, H.-M.; Thomas,M. L.; Ueno, K.; Thompson, C. V.; Dokko, K.; et al. Oxygen ReductionReaction in Highly Concentrated Electrolyte Solutions of LithiumBis(Trifluoromethanesulfonyl)Amide/Dimethyl Sulfoxide. J. Phys. Chem. C2017, 121 (17), 9162-9172; and Umebayashi, Y.; Mitsugi, T.; Fukuda, S.;Fujimori, T.; Fujii, K.; Kanzaki, R.; Takeuchi, M.; Ishiguro, S.-I.Lithium Ion Solvation in Room-Temperature Ionic Liquids InvolvingBis(Trifluoromethanesulfonyl) Imide Anion Studied by Raman Spectroscopyand DFT Calculations. J. Phys. Chem. B 2007, 111 (45), 13028-13032, eachof which is incorporated by reference in its entirety. Additionally, wenote that BMCF₃SA not only binds to Li⁺ more weakly than DMCF₃SA butalso has higher viscosity (Table S1), both of which contributed to itslower conductivity than DMCF₃SA.

The chemical stability of BTMSA, BMCF₃SA, and DMCF₃SA was evaluatedunder conditions mimicking the oxygen electrode of aprotic Li—O₂batteries using a previously established protocol. See, for example,Huang, M.; Feng, S.; Zhang, W.; Giordano, L.; Chen, M.; Amanchukwu, C.V.; Anandakathir, R.; Shao-Horn, Y.; Johnson, J. A. Fluorinated ArylSulfonimide Tagged (FAST) Salts: Modular Synthesis andStructure-property Relationships for Battery Applications. EnergyEnviron. Sci. 2018, which is incorporated by reference in its entirety.The solvents were mixed with 0.5 equivalent commercial lithium peroxide(Li₂O₂) and KO₂ powders; the mixtures were stirred and maintained at 80°C. for three days. The lack of appreciable change in the ¹H NMR spectracollected before and after the exposure to Li₂O₂ and KO₂ (FIG. 8)indicate that these solvents are highly resistant to chemicaldegradation by the oxygen reduction species, in good agreement with ourcomputational analyses (FIG. 6). In contrast, DMSO decomposedsignificantly under the same testing conditions to form dimethylsulfone, indicated by a strong peak around 3 ppm (FIG. 8). See, forexample, Weber, M.; Hellriegel, C.; Rueck, A.; Wuethrich, J.; Jenks, P.Using High-Performance 1H NMR (HP-QNMR®) for the Certification ofOrganic Reference Materials under Accreditation Guidelines—Describingthe Overall Process with Focus on Homogeneity and Stability Assessment.J. Pharm. Biomed. Anal. 2014, 93, 102-110; Weber, M.; Hellriegel, C.;Rueck, A.; Wuethrich, J.; Jenks, P. Using High-Performance 1H NMR(HP-QNMR®) for the Certification of Organic Reference Materials underAccreditation Guidelines—Describing the Overall Process with Focus onHomogeneity and Stability Assessment. J. Pharm. Biomed. Anal. 2014, 93,102-110, each of which is incorporated by reference in its entirety.

To evaluate the discharge characteristics and chemical stability ofthese electrolytes in real Li—O₂ battery environment, Li—O₂ cells withelectrolytes containing 0.2 M LiTFSI in BTMSA, BMCF₃SA, and DMCF₃SA,sandwiched by carbon paper with gas diffusion layer (CP-GDL) cathode andLi metal anode, were fully discharged with a voltage cutoff of 2.0V_(Li). Cells containing electrolyte solvents with higher DNs, BTMSA(16.9) and DMCF₃SA (16.4), exhibited higher full discharge capacities,1.04 and 0.95 mAh/cm², respectively, than the lower-DN solvent, BMCF₃SA(DN=13.3, full discharge capacity=0.79 mAh/cm²). This observation agreeswith the previously reported trend between higher-DN electrolyte andhigher discharge capacity in Li—O₂ batteries. XRD characterization ofthe CP-GDL cathodes after full discharge showed Li₂O₂, albeit ofrelatively low intensity, as the discharge product (FIG. 9 panel a). Theelectrolytes after full discharge were collected and analyzed by FTIR(FIG. 9 panel b), ¹H (FIG. 9 panel c) and ¹⁹F NMR (FIG. 9 panel d), andcompared to the pristine electrolytes. No perceivable change wasobserved in the FTIR or NMR spectra for all three electrolytes,indicating that these electrolytes are resistant to chemical degradationunder full discharge conditions.

Next, we evaluated the electrochemical stability of electrolytescontaining 0.1 M LiTFSI in BTMSA, BMCF₃SA, and DMCF₃SA usingpotentiostatic measurements, cyclic voltammetry (CV), and linear sweepvoltammetry (LSV). The potentiostatic measurements were performed underan oxygenated environment in a two-electrode electrochemical cell heldat various potentials from 3.4 to 5.0 V_(Li) for 3 hours each (FIG. 3,panel a). The electrochemical cell consists of a glass fiber separatorimpregnated with the electrolyte and sandwiched between stainless steelmesh (316) current collector and Li metal foil. The same measurement wasperformed on DMSO- and G4-based electrolytes as comparisons. Thesulfamide- and sulfonamide-based electrolytes exhibited desirableoxidative stability (oxidative current <5 μA, zoomed-in view in FIG. 3,panel b) at potentials ≤4.5 V_(Li), similar to the G4-based electrolyte(FIG. 10, panel a), whereas the cell containing DMSO showed oxidativecurrent that was 1˜2 orders of magnitude higher. At higher potentials(≥4.8 V_(Li), FIG. 3, panel c), sulfonamides with theelectron-withdrawing —CF₃ moiety, BMCF₃SA, and DMCF₃SA, exhibitedconsiderably greater electrochemical oxidative stability (oxidativecurrent <20 μA) than the sulfamide BTMSA (oxidative current 50˜220 μA),in great agreement with our computational prediction (FIG. 6). It hasbeen reported that carbon-based electrodes commonly-used in aproticLi—O₂ batteries can participate in parasitic reactions, especially athigh charging potential. See, for example, Gallant, B. M.; Mitchell, R.R.; Kwabi, D. G.; Zhou, J.; Zuin, L.; Thompson, C. V.; Shao-Horn, Y.Chemical and Morphological Changes of Li—O 2 Battery Electrodes uponCycling. J. Phys. Chem. C 2012, 116 (39), 20800-20805; Itkis, D. M.;Semenenko, D. A.; Kataev, E. Y.; Belova, A. I.; Neudachina, V. S.;Sirotina, A. P.; Havecker, M.; Teschner, D.; Knop-Gericke, A.; Dudin,P.; et al. Reactivity of Carbon in Lithium-Oxygen Battery PositiveElectrodes. Nano Lett. 2013, 13 (10), 4697-4701; McCloskey, B. D.;Speidel, A.; Scheffler, R.; Miller, D. C.; Viswanathan, V.; Hummelshøj,J. S.; Nørskov, J. K.; Luntz, A. C. Twin Problems of InterfacialCarbonate Formation in Nonaqueous Li—O 2 Batteries. J. Phys. Chem. Lett.2012, 3 (8), 997-1001; Ottakam Thotiyl, M. M.; Freunberger, S. A.; Peng,Z.; Bruce, P. G. The Carbon Electrode in Nonaqueous Li—O 2 Cells. J. Am.Chem. Soc. 2013, 135 (1), 494-500, each of which is incorporated byreference in its entirety. To investigate the electrochemical stabilityof the sulfamide- and sulfonamide-based electrolytes in the presence ofcarbon, we performed cyclic voltammetry (CV, 1 mV/s, 2.0-5.0 V_(Li),FIG. 11) tests in Ar and linear sweep voltammetry (LSV, 0.1 mV/s, fromopen circuit voltage to 5.0 V, FIG. 11 inset) tests in O₂ using CP-GDLas the working electrode. It is observed that, in both Ar and O₂, theBTMSA-based electrolyte started to exhibit increasing oxidative currentaround 4.2 V_(Li) in the presence of carbon electrode; nonetheless, inthe potentiostatic tests employing stainless steel current collector,this electrolyte only showed significant oxidative current atpotentials >4.5 V_(Li). On the other hand, similar to the potentiostaticmeasurements, the —CF₃ containing solvents, BMCF₃SA, and DMCF₃SA, showedsignificantly improved oxidative stability that is clearly superior tothe commercial reference DMSO at highly oxidizing potentials.

Differential electrochemical mass spectrometry (DEMS) have been employedto investigate the gas evolution on charge under galvanostaticconditions. Results for Li—O₂ cells using more electrochemically stableelectrolytes, DMCF₃SA, and BMCF₃SA compared to that of DMSO aresummarized in FIG. 4. Upon charge, the voltage profiles associated withDMSO-based cell increased steadily and reached a plateau around 4.3˜4.4V_(Li) (FIG. 4, panel a). The corresponding O₂ evolution rate initiallypeaked at ˜0.4 mol/h then gradually decayed, yielding an overallevolution of 2.74 μmol O₂; significant CO₂ evolution was observed forthe last 30% charging capacity (beginning at ˜4.3 V_(Li) and ˜0.2mAh/cm²). In contrast, the DMCF₃SA-based cell showed a long plateau at˜4.2 V_(Li) that was accompanied by a steady O₂ evolution rate of ˜0.4μmol/h (overall O₂ evolution=4.08 μmol), similar to the G4 cell as shownin FIG. 12; as the charging potential increased from 4.2 to 4.4 V_(Li),O₂ evolution significantly decreased while CO₂ evolution rapidlyincreased (FIG. 4, panel b). Interestingly, the charging potential ofthe BMCF₃SA-based cell increased slowly; the potential corresponding tothe first 70% charging capacity (˜0.2 mAh/cm²) remained below 3.9V_(Li), after which the voltage increased steadily to 4.3 V_(Li) (FIG.4, panel c). The O₂ evolution rate of the BMCF₃SA-based cell duringearly stage of charge was approximately twice as high as the DMSO-basedcell (˜0.6 vs. 0.3 μmol/h). As the potential of the BMCF₃SA-based cellincreased from 3.9 V_(Li) to 4.3 V_(Li), O₂ production increased againthen eventually diminished, evolving 4.42 μmol O₂ overall; CO₂ evolutionbecame dominant at >4.2 V_(Li). Li—O₂ cells employing 0.2 M LiTFSI inDMCF₃SA as the electrolyte were subject to prolonged galvanostaticcycling tests at 0.03 mA/cm² (capacity cutoff of 0.1 mAh/cm² unlessotherwise noted). The discharge-charge profiles of select cycles arepresented in FIG. 5, panel a. The electrolytes and positive electrodesof DMCF₃SA-based cells were collected after select cycles and analyzedusing ¹H NMR (FIG. 5, panel b, FIG. 13, panel a, and FIG. 14, panel a),¹⁹F NMR (FIG. 13, panel b and FIG. 14, panel b) as well as FTIR (FIG.13, panel c); the results are compared to DMSO- and G4-based cellscycled under the same galvanostatic conditions. The ¹H NMR analyses(FIG. 5, panel b) revealed clear new peaks for the DMSO-basedelectrolyte after the first cycle (capacity cutoff=0.3 mAh/cm²); thesignal attributable to dimethyl sulfone (DMSO₂) significantlyintensified after the 10^(th) cycle (˜2.9 ppm in FIG. 5, panel b andFIG. 14, panel a). G4 exhibited small amount of degradation product at˜3.7 ppm after 10 cycles (FIG. 5, panel b); after 92 cycles, however,numerous new peaks in the range of 3.6˜4.7 ppm (FIG. 5, panel b) as wellas a clear peak attributable to formate (˜8.1 ppm, FIG. 13, panel a)appeared. Our FTIR analyses also confirmed the presence of formate inG4-based electrolyte at ˜1700 cm-1 (FIG. 13, panel c). In contrast, theDMCF3SA-based electrolyte collected after the 1st (capacity cutoff=0.3mAh/cm²), 5th, 25th, and 92nd cycles appeared to be lack of appreciablenew peaks in the ¹H NMR (FIG. 5, panel b) and FTIR (FIG. 13, panel c)spectra, highlighting this solvent's desired stability under prolongedcycling conditions. Additionally, the ¹⁹F NMR analysis (FIG. 13, panelb) on the DMCF₃SA-based electrolyte showed negligible change for thefirst 25 cycles; nonetheless, the spectrum collected after 92 cyclesrevealed small amount of degradation products, likely resulting fromparasitic reactions with Li metal electrode and/or the oxygen electrode.

In summary, design of three sulfonamide-based solvents, BTMSA, BMCF₃SA,and DMCF₃SA, for chemical and electrochemical oxidative stability inaprotic Li—O₂ batteries is presented. The donor numbers (DNs) of thesesolvents were determined to be 13˜17 kcal/mol, and can dissolve lithiumsalts to show desirable conductivities; BTMSA-based electrolyteexhibited higher conductivity than that of tetraglyme (G4), BMCF₃SA, andDMCF₃SA. All three solvents were found to be stable in the presence ofcommercial Li₂O₂ and KO₂ powders at 80° C. for at least three days,showing superior chemical stability to DMSO. The electrochemicalstability of the sulfamide- and sulfonamide-based electrolytes wereevaluated using potentiostatic measurements, cyclic voltammetry (CV) andlinear sweep voltammetry (LSV) tests; all three solvents showed higherelectrochemical oxidative stability than DMSO. In particular, solventswith electron-withdrawing —CF₃ moiety, BMCF₃SA, and DMCF₃SA, were foundto be considerably stable against oxidation (V_(ox)>4.5 V_(Li)).Differential electrochemical mass spectrometry (DEMS) measurementsshowed O₂ as the vastly predominant gas evolved on charge; cellsemploying sulfonamide-based electrolytes exhibited ˜50% higher overallO₂ evolution than the DMSO cell. Li—O₂ cells employing DMCF₃SA-basedelectrolyte was cycled for 90 times without capacity decay. Resultspresented in this study demonstrate that sulfonamide-based solvents withthoughtfully designed molecular structures are promising candidates foraprotic Li—O₂ battery electrolytes.

FIG. 16 depicts synthetic schemes to compounds described herein.

FIGS. 17-19 depict properties of compounds described herein.

FIG. 20-21 depict polymers described herein.

FIGS. 22-23 depict synthetic schemes to compounds and polymers describedherein.

FIG. 24 depicts properties of polymers described herein.

FIG. 25 depicts synthetic schemes to compounds and polymers describedherein.

FIGS. 26-27 depict properties of polymers described herein.

FIGS. 28-29 depict properties of batteries with polymers describedherein, with different ratios of electrolyte to monomer groups.

FIG. 30 depicts synthetic schemes to compounds described herein.

FIG. 31 depicts properties of compounds described herein.

FIG. 32 depicts synthetic schemes to polymers described herein.

FIGS. 33-34 depict properties of polymers described herein.

FIG. 35 depicts synthetic schemes to polymers described herein.

FIGS. 36-38 depict properties of polymers described herein.

FIG. 39 depicts synthetic schemes to polymers described herein.

FIGS. 40-47 depict properties of polymers and batteries including thepolymers described herein.

FIG. 48 depicts a synthetic scheme and properties of polymers describedherein.

FIGS. 49-50 depict properties of polymers and batteries including thepolymers described herein.

FIG. 51 depicts properties of solvents described herein.

Details of one or more embodiments are set forth in the accompanyingdrawings and description. Other features, objects, and advantages willbe apparent from the description, drawings, and claims. Although anumber of embodiments of the invention have been described, it will beunderstood that various modifications may be made without departing fromthe spirit and scope of the invention. It should also be understood thatthe appended drawings are not necessarily to scale, presenting asomewhat simplified representation of various features and basicprinciples of the invention.

What is claimed:
 1. A composition comprising a polyolefin including aplurality of functional groups, the functional groups including anaprotic polar group selected from the group consisting of sulfamide,sulfoxy, carbonyl, phosphoramide or heterocyclic groups.
 2. Thecomposition of claim 1, wherein the polyolefin includes a polymer blockselected from the group consisting of:

wherein n is 1 to 100,000 and X is a functional group including one ormore sulfamide, sulfoxy, carbonyl, phosphoramide or heterocyclic groups,and Y is a bond or a C1-C6 alkyl or alkenyl optionally interrupted by O,S or NR, where NR is N—C1-C6 alkyl and including a moiety having one ormore functional group including sulfamide, sulfoxy, carbonyl,phosphoramide or heterocyclic groups.
 3. The composition of claim 1,wherein X is a monovalent or divalent moiety having a structure selectedfrom the group consisting of


4. The composition of claim 1, wherein Y is a bond.
 5. The compositionof claim 1, wherein Y is a C1-C6 alkyl or alkenyl optionally interruptedby O, S or NR, where NR is N—C1-C6 alkyl.
 6. The composition of claim 1,wherein the polyolefin includes a polymer block selected from the groupconsisting of:


7. A battery including a composition of claim
 1. 8. The battery of claim7, wherein the polyolefin includes a polymer block selected from thegroup consisting of:

wherein n is 1 to 100,000 and X is a functional group including one ormore sulfamide, sulfoxy, carbonyl, phosphoramide or heterocyclic groups,and Y is a bond or a C1-C6 alkyl or alkenyl optionally interrupted by O,S or NR, where NR is N—C1-C6 alkyl and including one or more functionalgroup including sulfamide, sulfoxy, carbonyl, phosphoramide orheterocyclic groups.
 9. The battery of claim 8, wherein the polyolefinincludes a polymer block selected from the group consisting of:


10. The battery of claim 8, further comprising a lithium saltelectrolyte.
 11. A battery including a solvent including an aproticpolar group.
 12. The battery of claim 11, wherein the aprotic polargroup includes sulfamide, sulfoxy, carbonyl, phosphoramide orheterocyclic groups.
 13. The battery of claim 11, wherein the aproticpolar group includes


14. The battery of claim 11, further comprising a lithium saltelectrolyte.